This contribution takes in account investigation of dental enamel regarding quality of hydroxyapatite material involved in the mineralization process. Areas damaged by black stain were investigated in order to evaluate changes in chemical composition as compared to those of healthy dental enamel. Different sectors on tooth surfaces were analyzed using micro-Raman spectroscopy. The integral areas of nu(1) (960cm(-1)) phosphate peak as well as of B-type carbonate peak nu(2) (1070cm(-1)) were obtained to investigate structural differences between the specimens (healthy/unhealthy enamel tooth and different sectors on unhealthy surface tooth). A complete list of chemical specimens involved in chemical processes on dental enamel surface was obtained by Energy Dispersive x-rays (EDX) investigation. It was noticed that mineralized carbonate peak at 1070cm(-1) decreased significantly for unhealthy tooth enamel or spots areas (as fluorite groups), suggesting that carbonate ions are easily dissolved in the presence of fluoride. The present study is confirming an organic origin for the dental black stain. The black stain is the result of a complex generation process from the damaged enamel, thus explaining their reappearance after the mechanical removing. A possible model for the black stain generation process is advanced.